Performic acid

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Performic acid
Skeletal structure of performic acid Performic Acid Structural Formula V.svg
Skeletal structure of performic acid
3D model of performic acid Performic-acid-3D-balls.png
3D model of performic acid
Names
Preferred IUPAC name
Methaneperoxoic acid [1]
Other names
Performic acid
Hydroperoxyformaldehyde
Formyl hydroperoxide
Permethanoic acid
Peroxyformic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.124.147 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 600-819-9
PubChem CID
UNII
  • InChI=1S/CH2O3/c2-1-4-3/h1,3H X mark.svgN
    Key: SCKXCAADGDQQCS-UHFFFAOYSA-N X mark.svgN
  • O=COO
Properties
CH2O3
Molar mass 62.024 g·mol−1
AppearanceColorless liquid
Melting point −18 °C (0 °F; 255 K) [2]
Boiling point 50 °C (122 °F; 323 K) (at 13.3 kPa; 90% pure acid) [2]
Acidity (pKa)7.1 [2] [3]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Performic acid (PFA) is an organic compound with the formula CH2O3. It is an unstable colorless liquid which can be produced by mixing formic acid with hydrogen peroxide. Owing to its oxidizing and disinfecting action, it is used in the chemical, medical and food industries.

Contents

Properties and applications

Performic acid is a colorless liquid soluble in water, alcohols, ether, benzene, chloroform and other organic solvents. [4] [5] Its strong oxidizing properties are used for cleaving disulfide bonds in protein mapping, [6] as well as for epoxidation, hydroxylation [7] and oxidation reactions in organic synthesis. [5] In the medical and food industries, performic acid is commonly used to disinfect equipment. It is effective against viruses, bacterial spores, algae, microscopic fungi and mycobacteria, as well as other microorganisms such as zooplankton.

The popularity of performic acid as a sterilizer originates from the safe nature of its degradation products, mostly carbon dioxide, oxygen and water. [4] [8] The disinfecting action of performic acid is also faster than that of the related compounds peracetic acid and hydrogen peroxide. [9] The major drawbacks of performic acid are handling dangers related to its high reactivity, as well as instability, especially upon heating, which means that the acid must be used within about 12 hours of it being synthesised. [9] [10] [11]

Synthesis

Performic acid is synthesized by the reaction of formic acid and hydrogen peroxide by the following equilibrium reaction:

Synthesis of Performic acid Performic acid Synthesis V2.svg
Synthesis of Performic acid

Synthesis of pure performic acid has not been reported, but aqueous solutions up to about 48% can be formed by simply mixing equimolar amounts of concentrated aqueous reactant solutions. [4] Using an excess of either reactant shifts the equilibrium towards the product side. The aqueous product solution can be distilled to increase the concentration of performic acid to about 90%. [4]

This reaction is reversible and can be used for large scale industrial production if accelerated with a catalyst; however, its temperature must be kept below 80–85 °C to avoid an explosion. [12] The catalyst can be nitric, hydrofluoric, phosphoric or sulfuric acid or their salts; [4] [13] it can also be an organic compound containing at least one ester group, such as carboxylic acid ester [14] or peracetic acid. [9]

Safety

Performic acid is non-toxic; it does irritate the skin, but less so than peracetic acid. Concentrated acid (above 50%) is highly reactive; it readily decomposes upon heating, and explodes upon rapid heating to 80–85 °C. It may ignite or explode at room temperature when combined with flammable substances, such as formaldehyde, benzaldehyde, or aniline, and explodes violently upon addition of metal powders. [4] For this reason, spilled performic acid is diluted with cold water and collected with neutral, non-flammable inorganic absorbents, such as vermiculite. [5]

Related Research Articles

<span class="mw-page-title-main">Catalysis</span> Process of increasing the rate of a chemical reaction

Catalysis is the increase in rate of a chemical reaction due to an added substance known as a catalyst. Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst.

<span class="mw-page-title-main">Hydrogen peroxide</span> Chemical compound

Hydrogen peroxide is a chemical compound with the formula H2O2. In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution in water for consumer use, and in higher concentrations for industrial use. Concentrated hydrogen peroxide, or "high-test peroxide", decomposes explosively when heated and has been used both as a monopropellant and an oxidizer in rocketry.

<span class="mw-page-title-main">Peroxide</span> Chemical compounds with the structure R–O–O–R

In chemistry, peroxides are a group of compounds with the structure R−O−O−R, where R is any element. The O−O group in a peroxide is called the peroxide group or peroxy group. The nomenclature is somewhat variable, and the term was introduced by Thomas Thomson in 1804 for an oxide with the greatest quantity of oxygen.

<span class="mw-page-title-main">Hydrogenation</span> Chemical reaction between molecular hydrogen and another compound or element

Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene. Catalysts are required for the reaction to be usable; non-catalytic hydrogenation takes place only at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

Hydroxylamine is an inorganic compound with the chemical formula NH2OH. The compound is in a form of a white hygroscopic crystals. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. The oxidation of NH3 to hydroxylamine is a step in biological nitrification.

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

<span class="mw-page-title-main">Hydrogen peroxide - urea</span> Chemical compound

Hydrogen peroxide - urea is a white crystalline solid chemical compound composed of equal amounts of hydrogen peroxide and urea. It contains solid and water-free hydrogen peroxide, which offers a higher stability and better controllability than liquid hydrogen peroxide when used as an oxidizing agent. Often called carbamide peroxide in dentistry, it is used as a source of hydrogen peroxide when dissolved in water for bleaching, disinfection and oxidation.

In organic chemistry, hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes from alkenes. This chemical reaction entails the net addition of a formyl group and a hydrogen atom to a carbon-carbon double bond. This process has undergone continuous growth since its invention: production capacity reached 6.6×106 tons in 1995. It is important because aldehydes are easily converted into many secondary products. For example, the resultant aldehydes are hydrogenated to alcohols that are converted to detergents. Hydroformylation is also used in speciality chemicals, relevant to the organic synthesis of fragrances and pharmaceuticals. The development of hydroformylation is one of the premier achievements of 20th-century industrial chemistry.

In chemistry, homogeneous catalysis is catalysis where the catalyst is in same phase as reactants, principally by a soluble catalyst a in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is an established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts.

Fenton's reagent is a solution of hydrogen peroxide (H2O2) and an iron catalyst (typically iron(II) sulfate, FeSO4). It is used to oxidize contaminants or waste water as part of an advanced oxidation process. Fenton's reagent can be used to destroy organic compounds such as trichloroethylene and tetrachloroethylene (perchloroethylene). It was developed in the 1890s by Henry John Horstman Fenton as an analytical reagent.

<span class="mw-page-title-main">Acid catalysis</span> Chemical reaction

In acid catalysis and base catalysis, a chemical reaction is catalyzed by an acid or a base. By Brønsted–Lowry acid–base theory, the acid is the proton (hydrogen ion, H+) donor and the base is the proton acceptor. Typical reactions catalyzed by proton transfer are esterifications and aldol reactions. In these reactions, the conjugate acid of the carbonyl group is a better electrophile than the neutral carbonyl group itself. Depending on the chemical species that act as the acid or base, catalytic mechanisms can be classified as either specific catalysis and general catalysis. Many enzymes operate by general catalysis.

<span class="mw-page-title-main">Organic peroxides</span> Organic compounds of the form R–O–O–R’

In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group. If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily breaks, producing free radicals of the form RO. Thus, organic peroxides are useful as initiators for some types of polymerization, such as the acrylic, unsaturated polyester, and vinyl ester resins used in glass-reinforced plastics. MEKP and benzoyl peroxide are commonly used for this purpose. However, the same property also means that organic peroxides can explosively combust. Organic peroxides, like their inorganic counterparts, are often powerful bleaching agents.

The Baeyer–Villiger oxidation is an organic reaction that forms an ester from a ketone or a lactone from a cyclic ketone, using peroxyacids or peroxides as the oxidant. The reaction is named after Adolf von Baeyer and Victor Villiger who first reported the reaction in 1899.

Peracetic acid (also known as peroxyacetic acid, or PAA) is an organic compound with the formula CH3CO3H. This peroxy acid is a colorless liquid with a characteristic acrid odor reminiscent of acetic acid. It can be highly corrosive.

<span class="mw-page-title-main">Dakin oxidation</span> Organic redox reaction that converts hydroxyphenyl aldehydes or ketones into benzenediols

The Dakin oxidation (or Dakin reaction) is an organic redox reaction in which an ortho- or para-hydroxylated phenyl aldehyde (2-hydroxybenzaldehyde or 4-hydroxybenzaldehyde) or ketone reacts with hydrogen peroxide (H2O2) in base to form a benzenediol and a carboxylate. Overall, the carbonyl group is oxidised, whereas the H2O2 is reduced.

The Milas hydroxylation is an organic reaction converting an alkene to a vicinal diol, and was developed by Nicholas A. Milas in the 1930s. The cis-diol is formed by reaction of alkenes with hydrogen peroxide and either ultraviolet light or a catalytic osmium tetroxide, vanadium pentoxide, or chromium trioxide.

Nickel boride is the common name of materials composed chiefly of the elements nickel and boron that are widely used as catalysts in organic chemistry. Their approximate chemical composition is Ni2.5B, and they are often incorrectly denoted "Ni
2
B
" in organic chemistry publications.

<span class="mw-page-title-main">Seleninic acid</span> Class of chemical compounds

A seleninic acid is an organoselenium compound and an oxoacid with the general formula RSeO2H, where R ≠ H. Its structure is R−Se(=O)−OH. It is a member of the family of organoselenium oxoacids, which also includes selenenic acids and selenonic acids, which are R−Se−OH and R−Se(=O)2−OH, respectively. The parent member of this family of compounds is methaneseleninic acid, also known as methylseleninic acid or "MSA".

Rhodium-platinum oxide , or Nishimura's catalyst, is an inorganic compound used as a hydrogenation catalyst.

<span class="mw-page-title-main">Trifluoroperacetic acid</span> Chemical compound

Trifluoroperacetic acid is an organofluorine compound, the peroxy acid analog of trifluoroacetic acid, with the condensed structural formula CF
3
COOOH
. It is a strong oxidizing agent for organic oxidation reactions, such as in Baeyer–Villiger oxidations of ketones. It is the most reactive of the organic peroxy acids, allowing it to successfully oxidise relatively unreactive alkenes to epoxides where other peroxy acids are ineffective. It can also oxidise the chalcogens in some functional groups, such as by transforming selenoethers to selones. It is a potentially explosive material and is not commercially available, but it can be quickly prepared as needed. Its use as a laboratory reagent was pioneered and developed by William D. Emmons.

References

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  2. 1 2 3 Elvers, B. et al. (ed.) (1991) Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. Vol. A19, Wiley, p. 206
  3. F. A. Carroll Perspectives on Structure and Mechanism in Organic Chemistry, Wiley-Interscience, 2010, ISBN   0-470-27610-X p. 416
  4. 1 2 3 4 5 6 Swern, Daniel (1949). "Organic Peracids". Chemical Reviews. 45: 1–68. doi:10.1021/cr60140a001. In the absence of catalysts, performic acid explodes when heated rapidly to 80–85°C.
  5. 1 2 3 Pradyot Patnaik A comprehensive guide to the hazardous properties of chemical substances, Wiley-Interscience, 2007, ISBN   0-471-71458-5, p. 128
  6. Simpson, R. J. (2007). "Performic Acid Oxidation of Proteins". Cold Spring Harbor Protocols. 2007 (3): pdb.prot4698. doi:10.1101/pdb.prot4698.
  7. "trans-1,2-CYCLOHEXANEDIOL". Organic Syntheses. 28: 35. 1948. doi:10.15227/orgsyn.028.0035.
  8. Gehr, R; Chen, D; Moreau, M (2009). "Performic acid (PFA): tests on an advanced primary effluent show promising disinfection performance" (PDF). Water Science and Technology. 59 (1): 89–96. doi:10.2166/wst.2009.761. PMID   19151490. Archived from the original (PDF) on 2010-11-16.
  9. 1 2 3 Preuss, A., Fuchs, R., Huss, M. & Schneider, R. 2001 Aqueous Disinfecting Agent Containing Performic Acid and Peracetic Acid Process for Production and Process for Use Thereof U.S. patent 6,211,237 , Issue date: April 3, 2001
  10. Bydzovska, O. & Merka, V. (1981). "Disinfecting Properties of Performic Acid Against Bacteriophage (X 174 as a Model of Small Envelope-free Viruses". J. Hygiene, Epidemiology Microbiology and Immunology. 25 (4): 414–423. PMID   6459365.
  11. Ripin, D.H.B.; et al. (2007). "Execution of a Performic Acid Oxidation on Multikilogram Scale". Org. Process Res. Dev. 11 (4): 762–765. doi:10.1021/op700039r.
  12. Elvers, B. et al. (ed.) (1991) Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. Vol. A12, Wiley, p. 16
  13. English, James; Gregory, J. Delafield (1947). "Performic Acid Hydroxylation of a,p-Unsaturated Acids and Esters". Journal of the American Chemical Society. 69: 2120. doi:10.1021/ja01201a016.
  14. Matilla, T. and Aksela, R. 2000 Method for the Preparation of Aqueous Solutions Containing Performic Acid as Well as Their Use. U.S. patent 6,049,002 , Issue date: April 11, 2000